Interaction of bentonite colloids with Cs, Eu, Th and U in presence of humic acid: A flow field-flow fractionation study

The interaction of Cs(I), Eu(III), Th(IV) and U(VI) with montmorillonite colloids was investigated in natural Grimsel Test Site groundwater over a 3 years period. The asymmetric flow field-flow fractionation combined with various detectors was applied to study size variations of colloids and to monitor colloid association of trace metals. The colloids suspended directly in the low ionic strength (I), slightly alkaline granitic groundwater (I = 10⁻³ mol/L, pH 9.6) showed a gradual agglomeration with a size distribution shift from initially 10-200 nm to 50-400 nm within over 3 years. The Ca²⁺ concentration of 2.1 × 10⁻⁴ mol/L in the ground water is believed to be responsible for the slow agglomeration due to Ca²⁺ ion exchange against Li⁺ and Na⁺ at the permanently charged basal clay planes. Furthermore, the Ca²⁺ concentration lies close to the critical coagulation concentration (CCC) of 10⁻³ mol L⁻¹ for clay colloids. Slow destabilization may delimit clay colloid migration in this specific groundwater over long time scales. Eu(III) and Th(IV) are found predominantly bound to clay colloids, while U(VI) prevails as the UO₂(OH)₃⁻ complex and Cs(I) remains mainly as aquo ion under our experimental conditions. Speciation calculations qualitatively represent the experimental data. A focus was set on the reversibility of metal ion-colloid binding. Addition of humic acid as a competing ligand induces rapid metal ion dissociation from clay colloids in the case of Eu(III) even after previous aging for about 3 years. Interestingly only partial dissociation occurs in the case of Th(IV). Experiments and calculations prove that the humate complexes dominate the speciation of all metal ions under given conditions. The partial irreversibility of clay bound Th(IV) is presently not understood but might play an important role for the colloid-mediated transport of polyvalent actinides over wide distances in natural groundwater.     

On magma fragmentation by conduit shear stress: Evidence from the Kos Plateau Tuff,Aegean Volcanic Arc

Large silicic explosive eruptions are the most catastrophic volcanic events. Yet, the intratelluric mechanisms underlying are not fully understood. Here we report a field and laboratory study of the Kos Plateau Tuff (KPT, 161 ka, Aegean Volcanic Arc), which provides an excellent geological example of conduit processes that control magma vesiculation and fragmentation during intermediate- to large-scale caldera-forming eruptions. A prominent feature of the KPT is the occurrence of quite unusual platy-shaped tube pumice clasts in pyroclastic fall and current deposits from the early eruption phases preceding caldera collapse. On macroscopic and SEM observations, flat clast faces are elongated parallel to tube vesicles, while transverse surfaces often occur at ~ 45° to vesicle elongation. This peculiar pumice texture provides evidence of high shear stresses related to strong velocity gradients normal to conduit walls, which induced vesiculation and fragmentation of the ascending magma. Either an increasing mass discharge rate without adequate enlargement of a narrow central feeder conduit or a developing fissure-like feeder system related to incipient caldera collapse provided suitable conditions for the generation of plate tube pumice within magma volumes under high shear during the pre-climactic KPT eruption phases. This mechanism implies that the closer to the conduit walls (where the stronger are the velocity gradients) the larger was the proportion of plate vs. conventional (lensoid) juvenile fragments in the ascending gas–pyroclast mixture. Consequently, plate pumice clasts were mainly entrained in the outer portions of the jet and convecting regions of a sustained, Plinian-type, eruption column, as well as in occasional lateral blast currents generated at the vent. As a whole, plate pumice clasts in the peripheral portions of the column were transported at lower altitudes and deposited by fallout or partial collapse closer to the vent relative to lensoid ones that dominated in the inner column portions. The plate tube pumice proportion decreased abruptly up to disappearance during the emplacement of the main pyroclastic currents and lithic-rich breccias related to extensive caldera collapse at the eruption climax, as a consequence of an overall widening of the magma feeder system through the opening of multiple conduits and eruptive vents, along with fissure erosion, concomitant to the disruption of the collapsing block.     

Chronology building using objective identification of annual signals in trace element profiles of stalagmites

Determination of annual lamination provides important additional constraints to radiometric dates on speleothems, both for dating the duration of specific growth intervals and optimizing growth models. In the absence of visible laminae, however, speleothem age models are reliant upon curve fitting through discretely dated points and are therefore inherently more uncertain than annual chronologies from laminae. Given that the impact of seasonality on speleothems is expected to be strong enough to generate an annual pulse in trace element chemistry regardless of whether or not visible or fluorescent growth laminae are visible, we demonstrate the potential for deriving high-resolution stalagmite chronologies from non-laminated samples using annual chemical variations in stalagmites from two Alpine caves (Obir, Austria and Ernesto, NE Italy). Trace element data were obtained by ion microprobe analyses for H, P, Mg, Na, Sr and Ba and the annual signal was sought using spectral and wavelet analysis. An automated chemical peak-counting software tool was developed in MATLAB^©. It counts significant annual peaks using criteria of minimum amplitude in relation to the local standard deviation of signal variation and minimum separation between peaks determined by the thickness of the preceding layers. Verification of the tool using visibly laminated samples suggests the software is a reliable and accurate method of chronology building, with hit ratios greater than 0.93 and less than 0.75% false alarm occurrences. Used in conjunction with other dating methods such as radiocarbon, U–Th and sulphur peak dating, the automated chemical laminae chronology-building approach provides a more meaningful alternative to simple age-depth curve fitting for non-laminated samples.     

Turbulence Closures In Neutral Boundary Layer Over Complex Terrain

In this work, three turbulence closure models, Mellor andYamada level 2.5, E - l and E - implemented in a circulation model, are compared in neutral condition over complex terrain. They are firstly applied to a one-dimensional case on flat terrain and then to a schematic two-dimensional valley. The simulation results, in terms of wind field and turbulent kinetic energy, are tested against measurements from a wind-tunnel experiment. The empirical constants defining the characteristic length scales of the closures are modified based on turbulence parameters estimated in the experiment. The formulation of the diffusion coefficients is analysed to explain the differences among the various closures in the simulation results. Regarding the mean flow, both on flat and complex terrain, all the closures yield satisfactory results. Concerning the turbulent kinetic energy, the best results are obtained by E - l and E - closures.     

1999年欧洲圣诞节风暴数值模拟分析

对1999年圣诞期间发生在欧洲中西部的圣诞节风暴进行了分析,认为4个主要的低气压系统中的第二个给法国北部带来了强风暴雨,巴黎的Orly机场阵风速度〉47m／s;第四个低压系统沿法国西海岸产生相似的恶劣天气,并在西班牙的北部海岸及地中海沿岸国家造成了毁灭性的破坏。在法国中部风暴最剧烈的时候,最大阵风〉41m／s;在法国和德国之间的区域,达55m／s。圣诞节风暴造成欧洲国家大约140人死亡,其他损失包括树木、街道和房屋被毁,电力系统和电话中断时间长达数天,受影响的人数大约为1000万,财产损失大约为80亿美元。由于风暴的极端强度和快速发展速度,欧洲大多数国家的数值预报中心没有对这次剧烈天气提供足够的预警。为此,利用中尺度数值预报系统（RAMS）模拟圣诞节风暴,并与ECMWF分析资料以及实况观测资料进行了对比分析。结果表明,RAMS模式能够准确模拟风暴的主要特性、低气压的演变和位置移动、发展的关键时间点、风暴演化期间的平均风场;模拟的平均风场和气象观测网的观测结果相一致;模拟的风暴移动时间和主要新闻媒体的报道相吻合;模式计算的一些特定地区平均风速的时间趋势显示,在阿尔卑斯山脉地区,无论是上风区还是下风区,风暴的时间都被准确地预测;模拟的第一次风暴最低气压值较实际值偏低。     

Geomaterials related to photovoltaics: a nanostructured Fe-bearing kuramite,Cu<Subscript>3</Subscript>SnS<Subscript>4</Subscript>

The successful synthesis of nanoparticles of Fe-bearing kuramite, (Cu,Fe)₃SnS₄, is reported in this study. Nanocrystalline powders were obtained through a mild, environmentally friendly and scalable solvothermal approach, in a single run. The sample was the object of a multidisciplinary investigation, including X-ray diffraction and absorption, scanning electron microscopy and microanalysis, electron paramagnetic resonance, diffuse reflectance and Mössbauer spectroscopy as well as SQUID magnetometry. The nanoparticles consist of pure Fe-bearing kuramite, exhibiting tetragonal structure. The valence state of the metal cations was assessed to be Cu⁺, Sn⁴⁺ and Fe³⁺. The material presents a band gap value of 1.6 eV, which is fully compatible with solar cell applications. The uptake of Fe by nanokuramite opens a compositional field where the physical properties can be tuned. We thus foster the application of Fe-bearing nanokuramite for photovoltaics and energy storage purposes.     

Isotopic and Elemental Composition of Marine Macrophytes as Biotracers of Nutrient Recycling Within a Coastal Lagoon in Baja California,Mexico

Nutrient sources of San Quintin Bay, a coastal lagoon affected by coastal upwelling off Baja California (Mexico), were traced using generalized additive (mixed) models (GAMM) to the stable nitrogen isotopic composition, C:N and N content of two co-occurring macrophytes (the macroalgae Ulva spp. and the seagrass Zostera marina). The geochemical tracers followed a spatial trend that partly responded to the long-term nutrient gradient from the ocean towards the interior of the bay. N content in Z. marina and Ulva spp. decreased linearly (while C:N increased) towards the middle section of the bay to concentration levels that indicate potential N limitation for growth. Concurrently midway into the bay (6–9 km), the δ¹⁵N of both macrophytes showed a gradual enrichment in ¹⁵N reflecting progressive denitrification. The spatial pattern of δ¹⁵N and the decrease in C:N of the macrophytes towards the innermost section of the bay indicated an additional nonoceanic source of dissolved nitrogen in this zone. The similarity of the δ¹⁵N pattern of Z. marina and Ulva spp. implies that their δ¹⁵N composition is mainly controlled by the availability of N, in spite of the physiological differences between taxa. A better fit of GAMM to N content and C:N was obtained for Z. marina than for Ulva spp. indicating that the former delineate more steadily and smoothly the influence of upwelling along the spatial gradient. Nonetheless, Ulva spp. may be analyzed in combination with Z. marina to characterize the environmental conditions at the time of sampling.