A Fe K-edge XAS study of amethyst

An X-ray absorption spectroscopy (XAS) study of the Fe local environment in natural amethyst (a variety of α-quartz, SiO₂) has been carried out. Room temperature measurements were performed at the Fe K-edge (7,112 eV), at both the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions. Experimental results were then compared with DFT calculations. XANES experimental spectra suggest Fe to occur mainly in the trivalent state, although a fraction of Fe²⁺ is identified. EXAFS spectra, on the other hand, reveal an unusual short distance for the first coordination shell:  = 1.78(2) Å, the coordination number being 2.7(5). These results allow to establish that Fe replaces Si in its tetrahedral site, and that numerous local distortions are occurring as a consequence of the presence of Fe³⁺ variably compensated by protons and/or alkaline ions, or uncompensated. The formal valence of Fe, on the basis of both experimental and DFT structural features, can be either 4+ or 3+. Taking into account the XANES evidences, we suggest that Fe mainly occurs in the trivalent state, compensated by protons, and that a minor fraction of Fe⁴⁺ is stabilised by the favourable local structural arrangement.     

The Geochemistry of Lake Joyce, McMurdo Dry Valleys, Antarctica

Lake Joyce is one of the least studied lakes of the McMurdo Dry Valleys. Similar to other lakes in this region, Lake Joyce is a closed-basin, permanently ice-covered, meromictic lake. We present here a detailed investigation of major ions, nutrients, and dissolved trace elements for Lake Joyce. Specifically, we investigate the role of iron and manganese oxides and hydrous oxides in trace metal cycling.Lake Joyce is characterized by fresh, oxic waters overlying an anoxic brine, primarily Na–Cl. Surface waters have a maximum nitrate concentration of 26M with a molar dissolved inorganic nitrogen to phosphorus ratio of 477. The supply of nitrogen is attributed to atmospheric deposition, possibly from polar stratospheric clouds. Dissolved phosphorus is scavenged by hydrous iron oxides. The pH is highest (10.15) just beneath the 7-m thick ice cover and decreases to a minimum of 7.29 in the redox transition zone. Dissolved Al exceeds 8M in surface waters, and appears to be controlled by equilibrium with gibbsite. In contrast, concentrations of other trace elements in surface waters are quite low (e.g., 5.4nM Cu, 0.19nM Co, <20pM La). Dissolved Fe, Mn, Ni and Cd were below our detection limits of 13 nM, 1. 8 nM, 4.7 nM and 15pM (respectively) in surface waters. There was a 6-m vertical separation in the onset of Mn and Fe reduction, with dissolved Mn appearing higher in the water column than Fe. Based on thermodynamic calculations, dissolved Mn appears to be controlled by equilibrium with hausmannite (Mn3O4). Co tracks the Mn profile closely, suggesting Co(III) is bound in the lattice of Mn oxides, whereas the Ce profile is similar, yet the Ce anomaly suggests oxidative scavenging of Ce. Release of Cu, Ni, Cd and trivalent REE appears to be controlled by pH-induced desorption from Fe and Mn oxides, although Cu (and perhaps Ni) may be scavenged by organic matter in surface waters.     

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.     

Tectono-sequence stratigraphy and U–Pb zircon ages of the Rincón Blanco Depocenter,northern Cuyo Rift,Argentina

Extensional processes that followed the Gondwanan Orogeny rise to the development of a series of rift basins along the continental margin over older accreted Eopaleozoic terranes. Stratigraphic, structural, paleontological, and isotopic studies are presented in this work in order to constrain the ages of the sedimentary infilling and to analyze the tectosedimentary evolution of one of the Cuyo basin depocenters, known as Rincón Blanco. This asymmetrical half-graben was filled by continental sediments under a strong tectonic control. The infilling was strongly controlled by tectonics which in term produced distinctive features along the whole sedimentary sequence. Using a combination of lithological and structural data the infilling was subdivided into packages of genetically linked units bounded by regional extended surfaces. Several tuffs and acid volcanic rocks have been collected across the whole section of the Rincon Blanco sub-basin for SHRIMP and LA-MC-ICPMS U–Pb zircon dating. The ages obtained range from 246.4 ± 1.1 Ma to 230.3 ± 1.5 Ma which is the time elapsed for the deposition of three tectono-sequence units separated by regional unconformities and mainly constrained to the Middle Triassic. They are interpreted as a result of a reactivation of the extensional system that has evolved along strike as segments of faults that linked together and/or as laterally propagating faults. Regional correlation with coeval rift basins permits to establish north-south propagation in the extensional regime along the western margin of SW Gondwana. This trending started in the lowermost Triassic and extended until the latest Triassic. Two of them were precisely correlated with Cerro Puntudo and Cacheuta half-graben systems. The new data indicate that the three sequences were mostly deposited during the Middle Triassic (246 to 230 Ma), with no evidence of sedimentation during Norian and Rhaetian, which is in conflict with some previous biostratigraphic studies.     

Epikarst hydrology and implications for stalagmite capture of climate changes at Grotta di Ernesto (NE Italy): results from long‐term monitoring

Grotta di Ernesto is a cave site well suited for palaeoclimate studies because it contains annually laminated stalagmites and was monitored from 1995 to the end of 2008 for microclimate, hydrology and hydrochemistry. Long‐term monitoring highlighted that cave drips show three different hydrological responses to rainfall and infiltration: (1) fast seasonal drips in the upper part of the cave, which are mostly fed by fractures, (2) slow seasonal drips, located at mid‐depth in the cave characterized by mixed feeding and (3) slow drips, mostly located in the deeper gallery, which are fed by seepage flow from bulk porosity with a minor fracture‐fed component. The slow drips display daily cycles during spring thaw. Monitoring also indicated that drip waters are only slightly modified by degassing within the soil zone and aquifer and by prior calcite precipitation. Hydrochemical studies show a clear seasonality in calcite saturation index, which results in most cave calcite precipitation occurring during late autumn and winter with similar amounts of precipitated calcite on most stalagmites, regardless of drip rate (discharge) differences. Drip rate, and drip rate variability, therefore, has a minor role in modulating the amount of annual calcite formation. In contrast, drip rate, when associated with moderate reduction in calcite saturation index, clearly influences stalagmite morphology. Increasing drip rate yields a passage from candle‐, to cone‐ to dome‐shaped stalagmites. Very high drip rates feed speleothems with flowstone morphology. In summary, monitoring provides information about the karst aquifer and how hydrology influences those physical and chemical characteristics of speleothems which are commonly used as climate proxies. Copyright © 2010 John Wiley & Sons, Ltd.     

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。     

Evolution of anthropogenic and biomass burning emissions of air pollutants at global and regional scales during the 1980�C2010 period

Several different inventories of global and regional anthropogenic and biomass burning emissions are assessed for the 1980?C2010 period. The species considered in this study are carbon monoxide, nitrogen oxides, sulfur dioxide and black carbon. The inventories considered include the ACCMIP historical emissions developed in support of the simulations for the IPCC AR5 assessment. Emissions for 2005 and 2010 from the Representative Concentration Pathways (RCPs) are also included. Large discrepancies between the global and regional emissions are identified, which shows that there is still no consensus on the best estimates for surface emissions of atmospheric compounds. At the global scale, anthropogenic emissions of CO, NO_x and SO₂ show the best agreement for most years, although agreement does not necessarily mean that uncertainty is low. The agreement is low for BC emissions, particularly in the period prior to 2000. The best consensus is for NO_x emissions for all periods and all regions, except for China, where emissions in 1980 and 1990 need to be better defined. Emissions of CO need better quantification in the USA and India for all periods; in Central Europe, the evolution of emissions during the past two decades needs to be better determined. The agreement between the different SO₂ emissions datasets is rather good for the USA, but better quantification is needed elsewhere, particularly for Central Europe, India and China. The comparisons performed in this study show that the use of RCP8.5 for the extension of the ACCMIP inventory beyond 2000 is reasonable, until more global or regional estimates become available. Concerning biomass burning emissions, most inventories agree within 50?C80%, depending on the year and season. The large differences between biomass burning inventories are due to differences in the estimates of burned areas from the different available products, as well as in the amount of biomass burned.     

Can agriculture support climate change adaptation, greenhouse gas mitigation and rural livelihoods? insights from Kenya

Changes in the agriculture sector are essential to mitigate and adapt to climate change, meet growing food demands, and improve the livelihoods of poor smallholder producers. What agricultural strategies are needed to meet these challenges? To what extent are there synergies among these strategies? This paper examines these issues for smallholder producers in Kenya across several agroecological zones. Several practices emerge as triple wins, supporting climate adaptation, greenhouse gas mitigation, and profitability goals. In particular, integrated soil fertility management and improved livestock feeding are shown to provide multiple benefits across all agroecological zones examined. Triple wins of other agricultural practices are limited to specific agroecological zones. Irrigation and soil and water conservation, for example, are essential for adaptation, mitigation, and profitability in arid areas. The results suggest that agricultural investments targeted toward these triple-win strategies will have the greatest payoff in terms of increased resilience of farm and pastoralist households and global climate change mitigation. To reap the benefits of triple-win strategies will require that policymakers, researchers, and practitioners move away from isolated approaches focused on either adaptation or mitigation or rural income generation toward a more holistic assessment of joint strategies as well as their tradeoffs and synergies.