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91.
Barry R. Bickmore Christopher J. Tadanier Will D. Monn 《Geochimica et cosmochimica acta》2004,68(9):2025-2042
Bond-valence methods for the prediction of (hydr)oxide solution monomer and surface functional group acidity constants are examined in light of molecular structures calculated using ab initio methods. A new method is presented that is based on these calculated structures, and it is shown that previously published methods have neglected one or more of four essential features of a generalized model. First, if the apparent pKa values of solution monomers are to be used to predict intrinsic pKa values of surface functional groups, similar electrostatic corrections must be applied in both cases. In surface complexation models, electrostatic corrections are applied by representing a charged surface as a uniform plane of charge density, and an analogous correction can be made to solution monomers by treating them as charged spheres. Second, it must be remembered that real surfaces and real monomers are not homogeneous planes or spheres. Rather, charge density is distributed rather unevenly, and a further electrostatic correction (which is often quite large) must be made to account for the proximity of electron density to the point of proton attachment. Third, the unsaturated valence of oxygen atoms in oxyacids, hexaquo cations, and oxide surfaces is strongly correlated with acidity after electrostatic corrections are made. However, calculation of unsaturated valence for oxyacids and oxide surfaces must be based on realistic MeO bond lengths (taking into account bond relaxation), which can be obtained from ab initio structure optimizations. Finally, unsaturated valence must be divided between possible bonds (four for oxygen atoms) to reflect the fact that O-H bonds are localized to particular regions of the O atoms.Empirical models that take all these factors into account are presented for oxyacids and hexaquo cations. These models are applied to the gibbsite (100), (010), (001), and cristobalite (100) surfaces, and it is demonstrated that the model for oxyacids predicts reasonable intrinsic pKa values for oxide surfaces. However, the prediction of surface pKa values is complex, because the protonation state of one functional group affects the pKa values of neighboring groups. Therefore, calculations of larger periodic systems, progressively protonated and reoptimized, are needed. 相似文献
92.
The development of gypsum maze caves under artesian conditions has been simulated. The numerical model simulations show that the evolution of maze caves in this type of setting requires structural preferences such as laterally extended fissure networks in a horizon of the gypsum layer. Without any structural preferences vertical shafts rather than maze caves are predicted to develop. The most important stage for the development of horizontal caves under artesian conditions is found to be the initial karstification period. During this period the structure of the mature conduit system is established. The solutional enlargement of conduits is spatially extended, total dissolution rates are higher than the later ones. 相似文献
93.
青藏高原腹地的内陆湖及其湖相沉积物能够较真实地反映气候变化特征,在高原环境变迁研究中备受中外科学家的关注.2006年8月15日~9月10日,中德联合考察小组对青藏高原东北部的冬给措纳湖一带进行了第四纪冻土、地貌和地质学考察,并对湖岸阶地做了初步的数字高程分析.调查了冬给措纳湖底地形、地貌,采集了湖相沉积物样本.在湖的东岸和西岸发现多年冻土,湖泊西北山谷观察到古冰川活动遗迹.初步推测该湖是由断陷沉降形成.为进一步分析湖区气候和环境变迁,联合小组拟定2007年3月份钻取湖芯. 相似文献
94.
95.
The paper compares pole figure determinations with neutron diffraction and X-ray diffraction on experimentally deformed carbonate rocks, a coarse grained marble and fine grained limestone. Neutron diffraction enables determination of complete pole figures on a single spherical specimen and is advantageous for coarse grained materials. Results obtained with both diffraction techniques agree satisfactorily, although uncertainties introduced by counting statistics are more serious for neutrons than for X-rays. Continuous detectors add new possibilities which are still little explored. 相似文献
96.
Gold mineralisation throughout about 45 Ma of Archaean orogenesis: protracted flux of gold in the Golden Mile, Yilgarn craton, Western Australia 总被引:1,自引:0,他引:1
The Golden Mile deposit was discovered in 1893 and represents today the largest Archaean orogenic lode gold system in the world (50 M oz produced gold). The Golden Mile deposit comprises three major styles of gold mineralisation: Fimiston, Oroya and Charlotte styles. Fimiston-style lodes formed at 250 to 350 °C and 100 to 200 MPa and are controlled by brittle–ductile fault zones, their subsidiary fault zone and vein networks including breccias and open-cavity-infill textures and hydrothermally altered wall rock. Fimiston lodes were formed late D1, prior to D2 regional upright folding. Hydrothermal alteration haloes comprise a progression toward the lode of diminishing chlorite, an increase in sericite and in Fe content of carbonates. Lodes contain siderite, pyrite, native gold, 17 different telluride minerals (Au–Ag tellurides contain ~25% of total gold), tourmaline, haematite, sericite and V-rich muscovite. Oroya-style lodes formed at similar P–T conditions as the Fimiston lodes and are controlled by brittle–ductile shear zones, associated dilational jogs that are particularly well developed at the contact between Paringa Basalt and black shale interflow sedimentary rocks and altered wall rock. The orebodies are characterised by micro-breccias and zones of intense shear zone foliation, very high gold grades (up to 100,000 g/t Au) and the common association of tellurides and vanadian mica (green leader). Oroya lodes crosscut Fimiston lodes and are interpreted to have formed slightly later than Fimiston lodes as part of one evolving hydrothermal system spanning D1 and D2 deformation (ca. 2,675–2,660 Ma). Charlotte-style lodes, exemplified by the Mt Charlotte deposit, are controlled by a sheeted vein (stockwork) complex of north-dipping quartz veins and hydrothermally altered wall rock. The Mt Charlotte orebody formed at 120 to 440 °C and 150 to 250 MPa during movement along closely spaced D4 (2,625 Ma) and reactivated D2 faults with the quartz granophyre in the Golden Mile Dolerite exerting a strong lithological control on gold mineralisation. Veins consist of quartz–carbonate–minor scheelite, and wall-rock alteration comprises chlorite destruction and growth of ferroan carbonate–sericite–pyrite–native gold. Pyrite–pyrrhotite is zoned on the scale of vein haloes and of the entire mine, giving a vertical temperature gradient of 50–100 °C over 1,000 vertical metres. The structural–hydrothermal model proposed consists of four major stages: (1) D1 thrusting and formation of Fimiston-style lodes, (2) D2 reverse faulting and formation of Oroya-style lodes, (3) D3 faulting and dissecting of Fimiston- and Oroya-style lodes, and (4) D4 faulting and formation of Mt Charlotte-style sheeted quartz vein system. The giant accumulation of gold in the Golden Mile deposit was formed due to protracted gold mineralisation throughout episodes of an Archaean orogeny that spanned about 45 Ma. Fluid conduits formed early in the tectonic history and persisted throughout orogenesis with the plumbing system showing a rare high degree of focussing, efficiency and duration. In addition to the long-lasting fluid plumbing system, the wide variety of transient structural and geochemical traps, multiple fluid sources and precipitation mechanism contributed towards the richest golden mile in the world.Editorial handling: B. Lehmann 相似文献
97.
Peter Haase Susanne Lohse Steffen Pauls Karin Schindehütte Andrea Sundermann Peter Rolauffs Daniel Hering 《Limnologica》2004,34(4):349-365
In the past, no single standardised method for sampling and sorting benthic macroinvertebrates has been implemented in Germany. Therefore, we tested the suitability of two common sorting protocols, RIVPACS and AQEM/STAR, by taking samples with each protocol at 44 sampling sites. Our results reveal that different methods deliver slightly different assessment results. Moreover these two methods differ in costs. Although the AQEM/STAR protocol takes longer than the RIVPACS protocol, we favoured the AQEM/STAR protocol because of its higher level of standardisation. In order to limit costs to an acceptable level, a modification of the AQEM/STAR protocol (MAS method) is developed. This method is highly standardised, gives stable assessment results and is relatively inexpensive (€ 224.00 for processing of an average sample). A detailed protocol of the newly developed method is given. 相似文献
98.
Robert Reinecke Alexander Wachholz Steffen Mehl Laura Foglia Christoph Niemann Petra Döll 《Ground water》2020,58(3):363-376
Global-scale gradient-based groundwater models are a new endeavor for hydrologists who wish to improve global hydrological models (GHMs). In particular, the integration of such groundwater models into GHMs improves the simulation of water flows between surface water and groundwater and of capillary rise and thus evapotranspiration. Currently, these models are not able to simulate water table depth adequately over the entire globe. Unsatisfactory model performance compared to well observations suggests that a higher spatial resolution is required to better represent the high spatial variability of land surface and groundwater elevations. In this study, we use New Zealand as a testbed and analyze the impacts of spatial resolution on the results of global groundwater models. Steady-state hydraulic heads simulated by two versions of the global groundwater model G3M, at spatial resolutions of 5 arc-minutes (9 km) and 30 arc-seconds (900 m), are compared with observations from the Canterbury region. The output of three other groundwater models with different spatial resolutions is analyzed as well. Considering the spatial distribution of residuals, general patterns of unsatisfactory model performance remain at the higher resolutions, suggesting that an increase in model resolution alone does not fix problems such as the systematic overestimation of hydraulic head. We conclude that (1) a new understanding of how low-resolution global groundwater models can be evaluated is required, and (2) merely increasing the spatial resolution of global-scale groundwater models will not improve the simulation of the global freshwater system. 相似文献
99.
Hubert J. Morel‐Seytoux Calvin D. Miller Cinzia Miracapillo Steffen Mehl 《Ground water》2017,55(3):399-407
Flow exchange between surface and groundwater is of great importance be it for beneficial allocation and use of water resources or for the proper exercise of water rights. In large‐scale regional studies, most numerical models use coarse grid sizes, which make it difficult to provide an accurate depiction of the phenomenon. In particular, a somewhat arbitrary leakance coefficient in a third type (i.e., Cauchy, General Head) boundary condition is used to calculate the seepage discharge as a function of the difference of head in the river and in the aquifer, whose value is often found by calibration. A different approach is presented to analytically estimate that leakance coefficient. It is shown that a simple equivalence can be deduced from the analytical solution for the empirical coefficient, so that it provides the accuracy of the analytical solution while the model maintains a very coarse grid, treating the water‐table aquifer as a single calculation layer. Relating the empirical leakance coefficient to the exact conductance, derived from physical principles, provides a physical basis for the leakance coefficient. Factors such as normalized wetted perimeter, degree of penetration of the river, presence of a clogging layer, and anisotropy can be included with little computational demand. In addition the river coefficient in models such as MODFLOW, for example, can be easily modified when grid size is changed without need for recalibration. 相似文献
100.
Method and Excel VBA Algorithm for Modeling Master Recession Curve Using Trigonometry Approach
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A new method was developed and implemented into an Excel Visual Basic for Applications (VBAs) algorithm utilizing trigonometry laws in an innovative way to overlap recession segments of time series and create master recession curves (MRCs). Based on a trigonometry approach, the algorithm horizontally translates succeeding recession segments of time series, placing their vertex, that is, the highest recorded value of each recession segment, directly onto the appropriate connection line defined by measurement points of a preceding recession segment. The new method and algorithm continues the development of methods and algorithms for the generation of MRC, where the first published method was based on a multiple linear/nonlinear regression model approach (Posavec et al. 2006). The newly developed trigonometry‐based method was tested on real case study examples and compared with the previously published multiple linear/nonlinear regression model‐based method. The results show that in some cases, that is, for some time series, the trigonometry‐based method creates narrower overlaps of the recession segments, resulting in higher coefficients of determination R2, while in other cases the multiple linear/nonlinear regression model‐based method remains superior. The Excel VBA algorithm for modeling MRC using the trigonometry approach is implemented into a spreadsheet tool (MRCTools v3.0 written by and available from Kristijan Posavec, Zagreb, Croatia) containing the previously published VBA algorithms for MRC generation and separation. All algorithms within the MRCTools v3.0 are open access and available free of charge, supporting the idea of running science on available, open, and free of charge software. 相似文献